Structural and Electronic-State Changes of a Sulfide Solid Electrolyte during the Li Deinsertion–Insertion Processes

Hakari, Takashi; Deguchi, Minako; Mitsuhara, Kei; Ohta, Toshiaki; Saito, Kohei; Orikasa, Yuki; Uchimoto, Yoshiharu; Kowada, Yoshiyuki; Hayashi, Akitoshi; Tatsumisago, Masahiro

doi:10.1021/acs.chemmater.7b00551

Cited by 162 publications

(175 citation statements)

References 65 publications

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“…In the delithiated phase, Li4PS5Cl, the S atoms at the 4a and 4c positions bond to the PS4 groups, demonstrated by a decrease in the intensity at r = 4.1 Å and an increase of intensity at r = 2.1 Å ( Fig. 3a), consistent with experimental observations where S bonds PS4 groups 19,20 . Because the PSx units move relative to each other in Li4PS5Cl, peak broadening occurs for r > 5 Å.…”

Section: Fig 2: Formation Energies Of Li-vacancy Configurations Of Lsupporting

confidence: 88%

“…4c,d). This indicates that the P-S-P bridges connecting the PS4 units, forming upon oxidation, break upon reduction transforming them back to isolated PS4 units, similar to what was reported for the Li3PS4 electrolyte 19,20,38 .…”

Section: Nmr Of Oxidative (A-c) and Reductive (D-f) Activity Of Lpsc supporting

confidence: 77%

“…These unstable argyrodite phases rapidly decompose into the expected stable Li3PS4, S and LiCl species after oxidation, and P, Li2S, and LiCl species after reduction. These decompose upon further oxidation and reduction to P2S7 -4 and S 0 at 2.9 V 31 and Li3P around 0.8 V 13,14 respectively, as observed by XPS 19,20 and the present XRD and NMR analysis. XRD and NMR also demonstrate the presence of metastable (de)lithiated argyrodite phases.…”

Section: Fig 6: Schematic Of the Electrochemical Activity Of Li6ps5csupporting

confidence: 52%

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Clarifying the relationship between redox activity and electrochemical stability in solid electrolytes

et al. 2020

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All-solid-state Li-ion batteries promise safer electrochemical energy storage with larger volumetric and gravimetric energy densities. A major concern is the limited electrochemical stability of solid electrolytes and related detrimental electrochemical reactions, especially because of our restricted understanding. Here we demonstrate for the argyrodite, garnet and NASICON type solid electrolytes, that the favourable decomposition pathway is indirect rather than direct, via (de)lithiated states of the solid electrolyte, into the thermodynamically stable decomposition products. The consequence is that the electrochemical stability window of the solid electrolyte is significantly larger than predicted for direct decomposition, rationalizing the observed stability window. The observed argyrodite metastable (de)lithiated solid electrolyte phases contribute to the (ir)reversible cycling capacity of all-solid-state batteries, in addition to the contribution of the decomposition products, comprehensively explaining solid electrolyte redox activity. The fundamental nature of the proposed mechanism suggests this is a key aspect for solid electrolytes in general, guiding interface and material design for all-solid-state batteries.3 All-solid-state-batteries (ASSBs) are attracting ever increasing attention due to their high intrinsic safety, achieved by replacing the flammable and reactive liquid electrolyte by a solid electrolyte 1 . In addition, a higher energy density in ASSBs may be achieved through; (a) bipolar stacking of the electrodes, which reduces the weight of the non-active battery parts and (b) by potentially enabling the use of a Li-metal anode, which possesses the maximum theoretical Li capacity and lowest electrochemical potential (3860 mAhg -1 and -3.04 V vs. SHE). First of all, the success of ASSBs relies on solid electrolytes with a high Li-ion conductivity 2-5 . A second prerequisite, is the electrochemical stability at the interfaces of the solid electrolyte with the electrode materials in the range of their working potentials. Any electrochemical decomposition of the solid electrolyte may lead to decomposition products with poor ionic conductivity that increase the internal battery resistance 2-4,6 . Third, ASSBs require mechanical stability as the changes in volume of the electrode materials upon (de)lithiation, as well as decomposition reactions at the electrode-electrolyte interface may lead to contact loss, also increasing the internal resistance and lowering the capacity 2-4 .

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Section: Fig 2: Formation Energies Of Li-vacancy Configurations Of Lsupporting

confidence: 88%

Section: Nmr Of Oxidative (A-c) and Reductive (D-f) Activity Of Lpsc supporting

confidence: 77%

Section: Fig 6: Schematic Of the Electrochemical Activity Of Li6ps5csupporting

confidence: 52%

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Clarifying the relationship between redox activity and electrochemical stability in solid electrolytes

et al. 2020

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“…Further the growth rate of the interphase layer between metallic lithium and Li 7 P 3 S 11 was estimated to (2.33 ± 0.22) × 10 −8 cm h −0.5 based on a parabolic rate law for diffusion‐controlled reactions, one order of magnitude lower than the growth rate for the interphases in LGPS . Moreover, during the charge/discharge, the PS 4 clusters in Li 3 PS 4 can be associated and dissociated in order to compensate the charge changes . Although it is reported in the first publication about LGPS that the electrochemical stability window obtained from cyclic voltammetry (CV) measurements is from 0 to 5 V, more and more studies have shown that the sulfide‐based SSEs possess quite narrow electrochemical window .…”

Section: Solid‐state Electrolytesmentioning

confidence: 98%

Progress of the Interface Design in All‐Solid‐State Li–S Batteries

Yue

Yan

Yin

et al. 2018

Adv Funct Materials

194

100

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Lithium-sulfur (Li-S) batteries are one of the most promising next-generation battery types for their high energy density and low cost. On the other hand, safety issues and poor cyclability strongly limit practical application. Solidstate electrolytes (SSEs) can present as high ionic conductivity as aprotic electrolytes and eventually avoid the shuttle effect, which provides an ultimate solution for safe Li-S batteries with good cyclability. In this review, the recent achievements in all-solid-state Li-S batteries based on inorganic SSEs are summarized. Furthermore, the main attentions are paid to the interfaces, including metallic lithium|SSEs, SSEs|SSEs, and composite sulfur cathode|SSEs. The potential approaches to deal with these interfacial issues are proposed as well, such as composite SSEs with an asymmetric structure to enhance their compatibility with lithium anodes and sulfur cathodes, adding Li 2 O or LiF and increasing the densification to reduce the grain boundary resistance, and nanomaterials used to improve the kinetic process in cathode. Figure 3. Structures of several SSEs. a) Local structure phase diagram of Li 2 S:P 2 S 5 glass ceramics and the changes of anionic units with temperature and compositions. Only the 75Li 2 S:25P 2 S 5 glass consisting of orthothiophosphates presents good thermal stability. Reproduced with permission. [58]

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“…In particular, the materials developed for sulfide‐ASSLBs, such as high conductivity electrolytes, surface stabilized active materials, and high energy density cathodes, which yielded noticeable improvements, have been very impressive . However, several significant challenges, in terms of electrode design, electrolyte chemical stability to air, and fabrication process, have hindered the practical application of ASSLBs . Therefore, in order to understand the current status of ASSLB development and determine the future research direction, it is highly necessary to compare the present sulfide‐ASSLBs with the conventional LIB technologies.…”

Section: Introductionmentioning

confidence: 99%

Advances and Prospects of Sulfide All‐Solid‐State Lithium Batteries via One‐to‐One Comparison with Conventional Liquid Lithium Ion Batteries

et al. 2019

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Owing to the safety issue of lithium ion batteries (LIBs) under the harsh operating conditions of electric vehicles and mobile devices, all‐solid‐state lithium batteries (ASSLBs) that utilize inorganic solid electrolytes are regarded as a secure next‐generation battery system. Significant efforts are devoted to developing each component of ASSLBs, such as the solid electrolyte and the active materials, which have led to considerable improvements in their electrochemical properties. Among the various solid electrolytes such as sulfide, polymer, and oxide, the sulfide solid electrolyte is considered as the most promising candidate for commercialization because of its high lithium ion conductivity and mechanical properties. However, the disparity in energy and power density between the current sulfide ASSLBs and conventional LIBs is still wide, owing to a lack of understanding of the battery electrode system. Representative developments of ASSLBs in terms of the sulfide solid electrolyte, active materials, and electrode engineering are presented with emphasis on the current status of their electrochemical performances, compared to those of LIBs. As a rational method to realizing high energy sulfide ASSLBs, the requirements for the sulfide solid electrolytes and active materials are provided along through simple experimental demonstrations. Potential future research directions in the development of commercially viable sulfide ASSLBs are suggested.

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Structural and Electronic-State Changes of a Sulfide Solid Electrolyte during the Li Deinsertion–Insertion Processes

Cited by 162 publications

References 65 publications

Clarifying the relationship between redox activity and electrochemical stability in solid electrolytes

Clarifying the relationship between redox activity and electrochemical stability in solid electrolytes

Progress of the Interface Design in All‐Solid‐State Li–S Batteries

Advances and Prospects of Sulfide All‐Solid‐State Lithium Batteries via One‐to‐One Comparison with Conventional Liquid Lithium Ion Batteries

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